Paper coated with a functional polyolefin film

ABSTRACT

The present invention relates to an article and a method for its preparation; the article comprises a cured polymeric film superposing paper or paperboard. The polymeric film is derived from a dispersion which comprises:
         a) a dispersant which is a copolymer with an acid value of 130 or less, comprising structural units of ethylene and a carboxylic acid monomer, wherein the copolymer has a melt flow index in the range of from 50 to 2000 g/10 min at 190° C./2.16 kg; wherein the weight-to-weight ratio of structural units of ethylene to carboxylic acid monomer is in the range of from 95:5 to 70:30; and wherein the dispersant has a concentration in the range of from 9 to 50 weight percent based on the weight of polymer solids in the dispersion;   b) a base polymer comprising non-functionalized ethylene-co-alkene copolymers, wherein the weight-to-weight ratio of the structural units of ethylene to alkene is in the range of from 99.8:0.2 to 50:50; and   c) a neutralizing agent which is a hard base and excludes an organic base having a boiling point of less than 250° C.; wherein the concentration of the neutralizing agent is sufficient to neutralize at least half of the carboxylic acid groups associated with the dispersion composition.       

     The article of the present invention is useful as a barrier to a wide range of hydrophobic and hydrophilic materials.

The present invention relates to an article comprising paper coated withan aqueous dispersion of polyolefin particles as well as paper coatedwith a polyolefin film arising from this dispersion.

Coating of paper or paperboard for use in a range of applications isknown to provide barriers to a wide range of substances including water,oil, and acids. Typically, high performance coatings, such as those usedfor paper drink cups, are prepared by extrusion coating or lamination ofa melted polyolefin resin directly onto the paper. This process providescontinuous coverage over the substrate and prevents liquid placed intothe cup from either contaminating the paper or soaking throughcompletely, thereby causing structural failure of the article.

Liquid applied barrier coatings for paper and paperboard have beendescribed in the art. United States Patent Publication 2006/0063877describes an aqueous dispersion of an olefin copolymer that is useful inpaper coating applications to improve brightness. United States PatentPublication 2016/0145806 discloses a dispersible ethylene-(meth)acrylicacid co-polymer for use as a water-repellency layer, requiring separatelayers to achieve a broad range of barriers to hydrophobic andhydrophilic materials.

United States Patent Publication 2018/0363248 discloses a way to preparea coated paper or paperboard with a relatively thin coating of anomniphobic barrier layer that maintains stain resistance to a widevariety of substances. The dispersion to form the omniphobic barrierlayer comprises water, a dispersant, a base polymer, and a neutralizingagent; wherein the dispersant is a copolymer comprising structural unitsof ethylene and a carboxylic acid monomer; wherein the base polymercomprises structural units of ethylene and a C₁-C₁₂-alkyl acrylate ormethacrylate; wherein the neutralizing agent is ammonia or an organicbase having a boiling point of less than 250° C.; and wherein theconcentration of the neutralizing agent is sufficient to neutralize atleast half of the carboxylic acid groups associated with the dispersant.

Alternative omniphobic barrier layers are needed that do not requireammonia or an organic base as a neutralizing agent and do not require abase polymer to comprise structural units of ethylene and a C₁-C₁₂-alkylacrylate or methacrylate. Emissions from ammonia or volatile organicbases are malodorous and can be subject to government regulations and/orhave safety issues related to exposure levels.

The present invention provides a process for preparing an omniphobicsingle layered coating onto paper or paperboard comprising the steps of:

-   -   a) applying onto paper or paperboard a dispersion composition        comprising water, a dispersant, a base polymer, and a        neutralizing agent; and    -   b) heating the composition to produce a cured film having a        thickness in the range of 1 to 20 g/m²;

-   wherein the sum of the dispersant and the base polymer comprise from    10 to 100 percent of the weight of polymer solids in the dispersion;    wherein

-   the dispersant is a copolymer with an acid value of 130 or less,    comprising structural units of ethylene and a carboxylic acid    monomer, wherein the copolymer has a melt flow index in the range of    from 50 to 2000 g/10 min at 190° C./2.16 kg; wherein the    weight-to-weight ratio of structural units of ethylene to carboxylic    acid monomer is in the range of from 95:5 to 70:30; and wherein the    dispersant has a concentration in the range of from 9 to 50 weight    percent based on the weight of polymer solids in the dispersion,    provided that the concentration of the dispersant in the composition    is sufficient to form a cured film with a Cobb value of less than 18    g/m² and oil contamination of less than 25 percent;

-   the base polymer comprises non-functionalized ethylene-co-alkene    copolymers, wherein the weight-to-weight ratio of the structural    units of ethylene to alkene is in the range of from 99.8:0.2 to    50:50; and

wherein the neutralizing agent is a hard base and excludes an organicbase having a boiling point of less than 250° C.; wherein theconcentration of the neutralizing agent is sufficient to neutralize atleast half of the carboxylic acid groups present in the dispersioncomposition.

The present invention further provides an article made according to theprocess of the present invention.

The composition, which is an aqueous dispersion comprising thedispersant, the base polymer, and the neutralizing agent may be preparedby a continuous or batch process. An example of a preferred continuousprocess is twin screw extrusion, as described in U.S. Pat. No.8,722,787, Comparative Example E. A batch process can be carried out,for example, using a 2CV Helicone mixer, which is a conical batch mixerthat uses dual intermeshing conical blades to mix high viscositymaterials. The concentration of polymers in the aqueous dispersion ispreferably in the range from 20, more preferably from 25, and mostpreferably from 30 weight percent, to preferably 60 and more preferablyto 55 weight percent, based on the weight of water and the polymerscombined.

The dispersant is a copolymer with an acid value of 130 or less,comprising structural units of ethylene and a carboxylic acid monomer,such as methacrylic acid, or itaconic acid. Preferably the dispersant isa copolymer comprising structural units of ethylene and methacrylic acid(EMAA). Preferably the dispersant has an acid value of less than 100.Most preferably the dispersant is EMAA with an acid value of 90-100. Theterm “acid value” refers to the mass of potassium hydroxide (KOH) inmilligrams that is required to neutralize one gram of copolymer and isdetermined by ASTM (D974). The term “structural unit” of the namedmonomer refers to the remnant of the monomer after polymerization. Forexample, a structural unit of methacrylic acid is as illustrated:

where the dotted lines represent the points of attachment of thestructural unit to the polymer backbone.

The dispersant copolymer has a melt flow index in the range of from 50to 2000 g/10 min at 190° C./2.16 kg (according to ASTM D1238) and theweight-to-weight ratio of structural units of ethylene to carboxylicacid monomer is in the range of from 95:5, preferably from 90:10, andmore preferably from 85:15 weight percent; to 70:30, and preferably to75:25 weight percent, based on the weight of the dispersant copolymer.The concentration of the dispersant is preferably in the range of from10, more preferably from 15 weight percent, more preferably from 25weight percent, preferably to 40, more preferably to 30 weight percent,based on the weight of polymer solids in the dispersion; provided thatthe concentration of the dispersant in the composition is sufficient toyield a cured film with a Cobb value of less than 18 g/m², preferablyless than 15 g/m² and more preferably less than 10 g/m² and oilcontamination of less than 25 percent, preferably less than 10 percent,more preferably less than 5 percent, most preferably 0 percent. Mostpreferably the concentration of the dispersant in the composition is inthe range of from 15 to 25 weight percent, based on the weight ofpolymer solids in the dispersion; provided that the concentration of thedispersant in the composition is sufficient to form a cured film with aCobb value as described. The concentration of the dispersant in thecomposition depends on the acid value of the dispersant, so that higheracid value dispersants require a lower concentration than lower acidvalue dispersants. When the dispersant has an acid value of 130, theconcentration of the dispersant in the composition is preferably up to20 weight percent, based on the weight of polymer solids in thedispersion. A suitable commercially available dispersant includesNUCREL™ 960 (an EMAA copolymer with an acid value of 98).

The base polymer comprises non-functionalized ethylene-co-alkenecopolymers, wherein the weight-to-weight ratio of the structural unitsof ethylene to alkene is in the range of from 99.8:0.2, preferably from99.7:0.3; and more preferably from 99.6:0.4; to 50:50, more preferablyto 60:40; and most preferably to 65:35. Preferred base polymers includeethylene-co-octene, ethylene-co-hexene, ethylene-co-butene copolymers,or mixtures thereof. Optionally the base polymer can also includefunctionalized ethylene copolymer comprising structural units of aC₁-C₁₂-alkyl acrylate or methacrylate; though preferably the basepolymer has no functionalized ethylene copolymer comprising structuralunits of a C₁-C₁₂-alkyl acrylate or methacrylate.

The concentration of base polymer in the composition is sufficient toform a cured film with a Cobb value of less than 18 g/m², preferablyless than 15 g/m² and more preferably less than 10 g/m² and oilcontamination of less than 25 percent, preferably less than 10 percent,more preferably less than 5 percent, most preferably 0 percent.Preferably, the concentration of the base polymer is preferably in therange of from 1, more preferably from 2, to 90, more preferably to 80,and most preferably to 75 weight percent, based on the weight of polymersolids in the dispersion. Commercial examples of base polymers include:ENGAGE™ 8200G (an ethylene octene copolymer having a melt index (190°C./2.16 Kg) of 5 g/10 min per ASTM D1238), ENGAGE™ 8401 (an ethyleneoctene copolymer having a melt index (190° C./2.16 Kg) of 30 g/10 minper ASTM D1238), AMPLIFY™ EA103 (a poly(ethylene-co-ethyl acrylate)copolymer with 19.5% ethyl acrylate and a melt index (190° C./2.16 Kg)of 21 g/10 min per ASTM D1238), AFFINITY™ EG8200G (an ethylene octenecopolymer having a melt index (190° C./2.16 Kg) of 5.0 g/10 min per ASTMD1238); all available from Dow, Inc. or its affiliates.

The neutralizing agent is a hard base, such as potassium hydroxide(KOH), sodium hydroxide (NaOH) and/or lithium hydroxide (LiOH) andexcludes an organic base having a boiling point of less than 250° C.,such as ammonia or an amine, N,N-dimethylethanolamine (DMEA),diethylamine, and morpholine. The concentration of neutralizing agent issufficiently high to neutralize at least half of the carboxylic acidgroups present in the dispersion composition. For example, if thedispersion composition comprises 0.05 mol of carboxylic acid groups in agiven mass, at least 0.025 mol of a hard base such as KOH would berequired. Thus, the molar ratio of basic functionality in theneutralizing agent to carboxylic acid groups in the dispersioncomposition is at least 0.5:1. Preferably the ratio is in the range offrom 0.7:1, more preferably from 0.9:1, to 1.4:1, to preferably 1.2:1,and more preferably to 1:1.

The composition may optionally comprise other components includingpolymeric coupling agents to improve the compatibility between thedispersant and the base polymer. An example of a suitable coupling agentincludes ethylene-co-maleic anhydride, which, when used, is present at aconcentration in the range of from 5 weight percent to 20, morepreferably to 10 weight percent based on the weight of polymer solids inthe dispersion. A commercial example of a coupling agent includes:LICOCENE™ 431 stabilized maleic anhydride grafted polyethylene wax(sometimes referred to as MA-g-PE), available from Clariant Corporationor its affiliates. It is expected that the amount of neutralizing agentwill be adjusted based on the total acid of the dispersion compositionwhen additional components are added.

The composition may optionally comprise up to 5 weight percent, basedthe weight of polymer solids in the dispersion, of a wax such asethylene bis(stearamide) and polyolefin waxes such as the commerciallyavailable POLYWAX™ 655 polyethylene available from Baker Hughes, Inc. orits affiliates, or ACRAWAX™ C (N,N′ethylene bisstearamide) availablefrom Lonza or its affiliates.

The composition may optionally be mixed or formulated with one or moreadditional components as those skilled in the art can appreciate, suchas for example, other water-based dispersions, pigments, wetting agents,defoamers, solvents, rheology modifiers, surfactants, anti-oxidants, andother processing aids to improve barrier and performance attributes ofthe coated paperboard. Such improvements include for example,compatibility with a substrate, dispersion wet out, coating flexibility,coating integrity upon exposure to extremes in temperature or radiation,flowablity, heat seal, and other attributes, as well as to lower cost inuse.

The composition can be applied to paper or paperboard using traditionalwet applications known to those skilled in the art, such as a wire wounddrawdown bar. The wet film can then heated to remove water, preferablyto a temperature in the range of from 50° C., more preferably from 70°C. to preferably 150° C., more preferably 120° C. to provide a coatweight of from 1, preferably from 2, more preferably from 4, and mostpreferably from 6 g/m², to 20, preferably to 15, more preferably to 12,and most preferably 10 g/m². The paper or paperboard may be uncoated orpre-coated.

A very thin layer of a film with low water uptake and high oilresistance (an omniphobic film) can be coated onto paper or paperboard;moreover, the application can be done in a single pass because theomniphobic properties are present in base polymer and the dispersant inthe applied aqueous composition. It has been surprisingly discoveredthat use of a hard base in combination with a copolymer dispersanthaving an acid value of 130 or less, particularly an EMAA copolymerdispersant, provides a polyolefin dispersion composition with excellentwater and oil barrier properties when applied and cured on paper andpaperboard without requiring the use of undesirable low boiling pointneutralizing agents. Additionally, such compositions do not necessarilyrequire functionalized ethylene copolymer comprising structural units ofa C₁-C₁₂-alkyl acrylate or methacrylate to provide coatings withoil/grease resistance and has no observed adhesion issues to pre-coatedpaper and board.

Sample Preparation

Coating formulations were prepared by applying polyolefin dispersioncompositions to an uncoated substrate. The substrate was 203 g/m²uncoated solid bleached sulphate (SBS) paperboard. Coatings of paper andpaperboard samples were prepared by hand using either a #10, #12, or #30wire-wound drawdown bar. Samples were cured in a Fisher ScientificIsotemp 180L Oven FA oven at 100° C. for 2 min.

Coat Weight Measurements

The coat weight of samples was measured by cutting out 7.17 in² (46.26cm²) sections coated and uncoated paper, then placing the sections in anoven at 100° C. for 2 min. All the samples were then weighed and thecoat weight was determined by the difference between the coated anduncoated samples.

Water Uptake Measurements

Water uptake testing was performed in a modified version of TAPPI methodT441 “Water absorptiveness of sized (non-bilious) paper, paperboard, andcorrugated fiberboard (Cobb test).” Samples of coated paper orpaperboard were prepared using the above method and then cut into 25-cm²round samples using a circular die and pneumatic press. A round samplewas placed in an oven at 100° C. for 2 min, then removed and weighed,then placed on a rubber mat; a circular metal ring was affixed on top ofthe round sample and clamped to prevent water leakage. Water at 90° C.was then poured over the sample to a height of 1 cm (25 mL of testliquid) and allowed to stand for 2 min. At the end of the test period,the test liquid was poured off and the coated sample was placed betweentwo sheets of blotter paper. A 10-kg metal roller was passed over thesample twice. Finally, the sample was weighed and the water uptake wascalculated based on the difference in mass between the exposed andunexposed sample. Cobb values are reported in units of g/m2. Cobb valuesof up to 18 g/m2 are reported as passing the test.

Oil and Grease Resistance Measurements

Oil and grease resistance of coatings was performed using a modifiedRalston Purina 2 test method. The coated paper or paperboard was cutinto a 2″×2″ square test sample and weighed. The test sample was placedon a sheet of standard graph paper with a ¼″ grid, which paper was fixedon a metal sheet. Two 1″ cotton flannel rounds saturated with vegetableoil were placed in the center of the coated paper or paperboard. Therounds were held in place by a brass weight with a diameter and a lengthof 1 inch. Samples of coated paper and paperboard cut to the samedimensions were also placed on the metal sheet to measure water loss bythe paper substrate during subsequent heat aging. The samples wereheat-aged in an oven at 60° C. for 24 h, after which time the sampleswere allowed to cool to room temperature. The weight and the cottonrounds were removed and excess oil was blotted off with a paper towel.Finally, the samples were weighed and the oil uptake (in g/m²) wascalculated based on mass difference correcting for water loss; the graphpaper was examined to determine the percentage of the squarescontaminated by oil break-through (referred to in the Table as “OGR %contamination”). Oil contamination values of less than 25 percent arereported as passing the test.

The examples and comparative example(s) utilize the followingcompositions: NUCREL™ 960 (an EMAA copolymer with an acid value of 98and melt index of 60 g/10 min @190° C./21.6 kg per ASTM D1238),available from Dow, Inc. or its affiliates; experimental EMAA copolymerA-2030 (an EMAA copolymer with an acid value of 130 and melt index of300 g/10 min @190° C./21.6 kg per ASTM D1238); experimental EMAAcopolymer B-X74 (an EMAA copolymer with an acid value of 98 and meltindex of 220 g/10 min @190° C./21.6 kg per ASTM D1238); PRIMACOR™ 5980icopolymer (an ethylene acrylic acid copolymer (20.5 wt % acrylic acid),which has a melt index of 300 g/10 minute per ASTM Method D1238 at 190°C./2.16 kg), available from SK Global Chemical Co., LTD. or itsaffiliates. AFFINITY EG™ 8200G (an ethylene octene copolymer having amelt index (190° C./2.16 Kg) of 5 g/10 min per ASTM D1238), ENGAGE™ 8401(an ethylene octene copolymer having a melt index (190° C./2.16 Kg) of30 g/10 min per ASTM D1238), AMPLIFY™ EA103 (a poly(ethylene-co-ethylacrylate) copolymer with 19.5% ethyl acrylate and a melt index (190°C./2.16 Kg) of 21 g/10 min per ASTM D1238); all available from Dow, Inc.or its affiliates; potassium hydroxide (KOH) and dimethylethanolamine(DMEA); LICOCENE™ 431 stabilized maleic anhydride grafted polyethylenewax (sometimes referred to as MA-g-PE), available from ClariantCorporation or its affiliates; and ACRAWAX™ C (N,N′ethylenebisstearamide) available from Lonza or its affiliates. Experimental EMAAcopolymers A and B may be prepared by standard free-radicalcopolymerization methods, using high pressure, operating in a continuousmanner Monomers are fed into the reaction mixture in a proportion whichrelates to the monomer's reactivity, and the amount desired to beincorporated. In this way, uniform, near-random distribution of monomerunits along the chain is achieved. Polymerization in this manner is wellknown and is described for example, in U.S. Pat. No. 4,351,931(Armitage).

EXAMPLES Example 1 Preparation of an Aqueous Dispersion of Amplify™EA103 Base Polymer, Dispersant, Polymeric Coupling Agent, Wax andEngage™ 8401 Base Polymer at a 5:15:10:1.5:68.5 w/w/w/w/w Ratio

Amplify™ EA103 (5 weight percent of polymer solids), Nucrel™ 960 (15weight percent of polymer solids), MA-g-PE (10 weight percent of polymersolids), Acrawax™ C (1.5 weight percent of polymer solids) and Engage™8401 (68.5 weight percent of polymer solids) were fed individually andconcurrently from separate hoppers at the specified relative weights ata rate of 10 lbs/h (4.5 kg/h) into a 25 mm Bersdorff™ ZE25 UTX extruderwith 48 L/D (rotating at 450 rpm). The extruder temperature profile wasramped to 150° C. prior to the introduction, through ISCO pumps, ofwater (21.3 mL/min at 123° C. and 346 psi) and

30 wt % KOH (3.4 mL/min) separately and concurrently. Dilution water (80mL/min at 123° C. and 550 psi) was then added and the mixture was cooledto 97° C. at the extruder outlet. A back-pressure regulator was used atthe extruder outlet to adjust the pressure in the extruder barrel toreduce steam formation. The resulting dispersion was cooled and filteredthrough a 200-μm filter and deemed good quality based on low gritretention (<100 ppm), colloidal stability (no phase separation with 48hours of production), dispersion solids (close to percent solids addedto extruder) and particle size (<3 μm, as determined using a CoulterLS320 particle size analyzer or comparable tool)).

Example 2 Preparation of an Aqueous Dispersion of Base Polymer andDispersant at a 80/20 w/w Ratio

ENGAGE™ 8200 (80 weight percent of polymer solids) and experimentalcopolymer B-X74 (20 weight percent of polymer solids) were fedindividually and concurrently from separate hoppers at the specifiedrelative weights at a rate of 10 lbs/h (4.5 kg/h) into a 25 mmBersdorff™ ZE25 UTX extruder with 48 L/D (rotating at 450 rpm). Theextruder temperature profile was ramped to 140° C. prior to theintroduction, through ISCO pumps, of water (17.5 mL/min at 117° C. and211 psi) and 30 wt % KOH (3.27 mL/min) separately and concurrently.Dilution water (100 mL/min at 127° C. and 86 psi) was then added. Aback-pressure regulator was used at the extruder outlet to adjust thepressure in the extruder barrel to reduce steam formation. The resultingdispersion was cooled and filtered through a 200-μm filter.

Example 3 utilizes the procedure of Example 1, but without Amplify™EA103 and with the components as shown in Table 1. Examples 4-6 utilizethe procedure of Example 2 with the components as shown in Table 1.

Example 7 Preparation of an Aqueous Dispersion of Base Polymer andDispersant at a 60/40 w/w Ratio

AFFINITY™ EG8200G (60 weight percent of polymer solids) and NUCREL™ 960(40 weight percent of polymer solids) were fed individually andconcurrently from separate hoppers at the specified relative weights ata rate of 600 lbs/h (272 kg/h) into a 58 mm Coperion™ ZSK extruder with48 L/D (rotating at 1110 rpm). The extruder temperature profile wasramped to 150° C. prior to the introduction, through ISCO pumps, ofwater (2.55 L/min at 113° C. and 310 psi) and 30 wt % KOH (0.35 L/min)separately and concurrently. Dilution water (5.12 L/min at 117° C. and310 psi) was then added and the mixture was cooled to 101° C. at theextruder outlet. A back-pressure regulator was used at the extruderoutlet to adjust the pressure in the extruder barrel to reduce steamformation. The resulting dispersion was then further cooled to 34° C.through an in line cooler.

Example 8 Preparation of an Aqueous Dispersion of Base Polymer andDispersant at a 85/15 w/w Ratio

AFFINITY™ EG8200G (85 weight percent of polymer solids) and experimentalcopolymer A (15 weight percent of polymer solids) were fed individuallyand concurrently from separate hoppers at the specified relative weightsat a rate of 10 lbs/h (4.5 kg/h) into a 25 mm Bersdorff™ ZE25 UTXextruder with 48 L/D (rotating at 450 rpm). The extruder temperatureprofile was ramped to 140° C. prior to the introduction, through ISCOpumps, of water (10.65 mL/min at 94° C. and 210 psi) and 30 wt % KOH(3.26 mL/min) separately and concurrently. Dilution water (100 mL/min at86° C. and 500 psi) was then added. A back-pressure regulator was usedat the extruder outlet to adjust the pressure in the extruder barrel toreduce steam formation. The resulting dispersion was cooled and filteredthrough a 200-μm filter.

Examples 9-12 utilize the procedure of Example 7 with the components asshown in Table 1.

Example 13—Preparation of an Aqueous Dispersion of Amplify™ EA103 BasePolymer, Dispersant, Polymeric Coupling Agent, Wax and Engage™ 8401 BasePolymer at a 5:8:10:1.5:75.5 w/w/w/w/w Ratio EA103 (5 weight percent ofpolymer solids), PRIMACOR™ 5980i (8 weight percent of polymer solids),MA-g-PE (10 weight percent of polymer solids), Acrawax™ C (1.5 weightpercent of polymer solids) and 8401 (75.5 weight percent of polymersolids) were fed individually and concurrently from separate hoppers atthe specified relative weights at a rate of 10 lbs/h (4.5 kg/h) into a25 mm Bersdorff™ ZE25 UTX extruder with 48 L/D (rotating at 450 rpm).The extruder temperature profile was ramped to 150° C. prior to theintroduction, through ISCO pumps, of water (7.7 mL/min at 115° C. and250 psi) and 30 wt % KOH (3.1 mL/min) separately and concurrently.Dilution water (80 mL/min at 104° C. and 550 psi) was then added and themixture was cooled to 97° C. at the extruder outlet. A back-pressureregulator was used at the extruder outlet to adjust the pressure in theextruder barrel to reduce steam formation. The resulting dispersion wascooled and filtered through a 200-μm filter.

Examples 14-17 utilize the procedure of Example 13 with the componentsas shown in Table 1.

Example 18 Preparation of an Aqueous Dispersion of Base Polymer andDispersant at a 60/40 w/w Ratio

AFFINITY™ EG8200 (60 weight percent of polymer solids) and PRIMACOR™5980 (40 weight percent of polymer solids) were fed individually andconcurrently from separate hoppers at the specified relative weights ata rate of 600 lbs/h (272 kg/h) into a 58 mm Coperion™ ZSK extruder with48 L/D (rotating at 1110 rpm). The extruder temperature profile wasramped to 150° C. prior to the introduction, through ISCO pumps, ofwater (0.79 L/min at 109° C. and 312 psi) and 30 wt % KOH (0.64 L/min)separately and concurrently. Dilution water (5.24 L/min at 106° C. and312 psi) was then added and the mixture was cooled to 101° C. at theextruder outlet. A back-pressure regulator was used at the extruderoutlet to adjust the pressure in the extruder barrel to reduce steamformation. The resulting dispersion was then further cooled to 37Cthrough an in line cooler.

Example 19 Preparation of an Aqueous Dispersion of Amplify™ EA 103 BasePolymer, Dispersant, Polymeric Coupling Agent, Wax and Engage™ 8401 BasePolymer at a 5:15:10:1.5:68.5 w/w/w/w/w Ratio

Amplify™ EA103 (5 weight percent of polymer solids), Nucrel™ 960 (15weight percent of polymer solids), MA-g-PE (10 weight percent of polymersolids), Acrawax™ C (1.5 weight percent of polymer solids) and Engage™8401 (68.5 weight percent of polymer solids) were fed individually andconcurrently from separate hoppers at the specified relative weights ata rate of 10 lbs/h (4.5 kg/h) into a 25 mm Bersdorff™ ZE25 UTX extruderwith 48 L/D (rotating at 450 rpm). The extruder temperature profile wasramped to 130° C. prior to the introduction, through ISCO pumps, ofwater (13.85 mL/min at 28° C. and 501 psi) and 100 wt % DMEA (3.88mL/min) separately and concurrently. Dilution water (110 mL/min at 21°C. and 600 psi) was then added. A back-pressure regulator was used atthe extruder outlet to adjust the pressure in the extruder barrel toreduce steam formation. The resulting dispersion was cooled and filteredthrough a 200-μm filter. This filtration operation proceeded much moreslowly than the other examples, and 18% of the added solids was removedduring the filtration. Both of these results are indicative of a verypoor quality dispersion. The quality of all previous dispersion examplescould be described as good.

Example 20 utilizes the procedure of Example 19 with the components asshown in Table 1. As with Example 19, filtration proceeded very slowly,but there was no corresponding removal of large amounts of polymersolids. This dispersion was considered poor in quality due to highlevels of grit (>100 ppm), dispersion solids (25% lower than solidsadded to extruder) and particle size (>10 μm).

Table 1 illustrates a summary of the sample compositions

TABLE 1 Sample Compositions Dispersant Dispersant Dispersant Ex.Components Composition Base DoN Comonomer Acid value Wt. % 1 Engage8401/ 68.5/5/10/15/1.5 KOH 90% EMAA 98 15 Amplify EA103/ Licocene 431/Nucrel 960/ Acrawax C 2 Engage 8200/ 80/20 KOH 85% EMAA 98 20 B-X74 3Engage 8401/ 68.5/10/20/1.5 KOH 90% EMAA 98 20 Licocene 431/ Nucrel 960/Acrawax C 4 Engage 8200/ 75/25 KOH 85% EMAA 98 25 B-X74 5 Engage 8200/70/30 KOH 85% EMAA 98 30 B-X74 6 Engage 8200/ 65/35 KOH 85% EMAA 98 35B-X74 7 Affinity EG8200/ 60/40 KOH 85% EMAA 98 40 Nucrel 960 8 AffinityEG8200/ 85/15 KOH 85% EMAA 130 15 A-2030 9 Affinity EG8200/ 80/20 KOH85% EMAA 130 20 A-2030 10 Affinity EG8200/ 75/25 KOH 85% EMAA 130 25A-2030 11 Affinity EG8200/ 70/30 KOH 85% EMAA 130 30 A-2030 12 AffinityEG8200/ 60/40 KOH 85% EMAA 130 40 A-2030 13 Engage 8401/ 75.5/5/10/8/1.5KOH 90% EAA 155 8 Amplify EA103/ Licocene 431/ PRIMACOR 5980i/ Acrawax C14 Engage 8401/ 73/5/10/10/1.5 KOH 90% EAA 155 10 Amplify EA103/Licocene 431/ PRIMACOR 5980i/ Acrawax C 15 Engage 8401/ 71/5/10/12.5/1.5KOH 90% EAA 155 12.5 Amplify EA103/ Licocene 431/ PRIMACOR 5980i/Acrawax C 16 Engage 8401/ 68.5/5/10/15/1.5 KOH 90% EAA 155 15 AmplifyEA103/ Licocene 431/ PRIMACOR 5980i/ Acrawax C 17 Engage 8401/45.5/18/10/25/1.5 KOH 80% EAA 155 25 Amplify EA103/ Licocene 431/PRIMACOR 5980i/ Acrawax C 18 Affinity EG8200/ 60/40 KOH 85% EAA 155 40PRIMACOR 5980i 19 Engage 8401/ 68.5/5/10/15/1.5 DMEA 150%  EMAA 98 15Amplify EA103/ Licocene 431/ Nucrel 960/ Acrawax C 20 Engage 8401/68.5/5/10/15/1.5 DMEA 90% EMAA 98 15 Amplify EA103/ Licocene 431/ Nucrel960/ Acrawax C DoN means Degree of Neutralization

Water Uptake and Oil/Grease Resistance Testing

All samples were cured at 100° C. for 2 min. All Cobb data was generatedat 90° C. water for 2 min. The target Cobb value for water uptake was<10 g/m². The target value for oil uptake was <15 g/m² and the targetvalue for contamination was 0%. Table 2 illustrates the coat weights,Cobb values, oil uptake values and contamination percentage results forall the samples.

TABLE 2 Water Uptake and Oil/Grease Resistance Results Coat Wt Cobb CobbOGR OGR % Ex g/m2 Pass/Fail g/m2 Pass/Fail contamination 1 11 Pass 7Pass 0% 2 7 Pass 6 Pass 0% 3 11 Pass 4 Pass 0% 4 8 Pass 7 Pass 0% 5 8Pass 7 Pass 0% 6 10 Pass 6 Pass 0% 7 8 Pass 5 Pass 0% 8 8 Pass 7 Pass 0%9 8 Pass 10 Pass 0% 10 6 Fail 27 Pass 0% 11 9 Fail 50 Pass 0% 12 19 Fail94 Pass 0% 13 11 Pass 12 Fail 100%  14 12 Pass 10 Fail 100%  15 12 Fail49 Fail 100%  16 10 Fail 82 Fail 67%  17 8 Fail 160 Pass 0 18 8 Fail 209Pass 6.3%  19 11 Pass 4.2 Fail 63%  20 14 Pass 5.7 Fail 100% 

Examples 1, 19 and 20 results show that the use of KOH in place of DMEAin the dispersion improves performance characteristics of the coatedpaperboard. Table 1 shows the importance of the dispersant acid valueand the total amount of acid in the dispersion on properties of thecoated paperboard.

What is claimed is:
 1. A process for preparing an omniphobic singlelayered coating onto paper or paperboard comprising the steps of: a)applying onto paper or paperboard a dispersion composition comprisingwater, a dispersant, a base polymer, and a neutralizing agent; and b)heating the composition to produce a cured film having a thickness inthe range of 1 to 20 g/m²; wherein the sum of the dispersant and thebase polymer comprise from 10 to 100 percent of the weight of polymersolids in the dispersion; wherein the dispersant is a copolymer with anacid value of 130 or less, comprising structural units of ethylene and acarboxylic acid monomer, wherein the copolymer has a melt flow index inthe range of from 50 to 2000 g/10 min at 190° C./2.16 kg; wherein theweight-to-weight ratio of structural units of ethylene to carboxylicacid monomer is in the range of from 95:5 to 70:30; and wherein thedispersant has a concentration in the range of from 9 to 50 weightpercent based on the weight of polymer solids in the dispersion,provided that the concentration of the dispersant in the composition issufficient to form a cured film with a Cobb value of less than 18 g/m²and oil contamination of less than 25 percent; the base polymercomprises non-functionalized ethylene-co-alkene copolymers, wherein theweight-to-weight ratio of the structural units of ethylene to alkene isin the range of from 99.8:0.2 to 50:50; and wherein the neutralizingagent is a hard base and excludes an organic base having a boiling pointof less than 250° C.; wherein the concentration of the neutralizingagent is sufficient to neutralize at least half of the carboxylic acidgroups present in the dispersion composition.
 2. The process of claim 1wherein the cured film has a thickness in the range of from 2 to 12g/m²; wherein the dispersant is a copolymer of ethylene and methacrylicacid; the base polymer is ethylene-co-octene, ethylene-co-hexene,ethylene-co-butene copolymers, or mixtures thereof; and the neutralizingagent is potassium hydroxide.
 3. The process of claim 2 wherein thecured film has a thickness in the range of from 4 to 10 g/m², whereinthe concentration of structural units of ethylene to structural units ofmethacrylic acid in the dispersant is in the range of from 99.5:0.5 to75:25; the concentration of the dispersant in the composition is in therange of from 10 to 40 percent based on the weight of polymer solids inthe dispersion; and wherein the concentration of the base polymer in thecomposition is in the range of from 50 to 90 percent based on the weightof polymer solids in the dispersion.
 4. The process of claim 1 whereinthe concentration of base polymer is sufficient to form a cured filmwith a Cobb value of less than 10 g/m² and oil contamination of lessthan 5%.
 5. The process of claim 4 wherein the concentration of basepolymer is in the range of from 2 to 75 weight percent, based on theweight of polymer solids in the dispersion.
 6. The process of claim 1wherein the composition further comprises from 5 to 10 weight percent ofa polymeric coupling agent, based on the weight of polymer solids in thedispersion.
 7. The process of claim 5 wherein the base polymer of thecomposition has no copolymer comprising structural units of ethylene anda C₁-C₁₂-alkyl acrylate or methacrylate.
 8. The process of claim 5wherein the composition further comprises up to 5 weight percent of awax, based on the weight of polymer solids in the dispersion.
 9. Anarticle made according to the process of claim 1.